JP2021038343A - Method for producing highly conductive composite, method for producing organic solvent dispersion of highly conductive composite, conductive film, and method for producing the same - Google Patents

Abstract

To provide a method for producing a highly conductive composite excellent in production efficiency, a method for producing an organic solvent dispersion of a highly conductive composite, a conductive film, and a method for producing the same.SOLUTION: The method for producing a highly conductive composite includes: obtaining a mixed liquid prepared by mixing an aqueous dispersion of a conductive composite containing a π-conjugated conductive polymer and a polyanion with an organic solvent; depositing a highly conductive composite in the mixed liquid; and then adding an epoxy compound to the mixed liquid, thereby collecting the highly conductive composite to which the epoxy compound has been added.SELECTED DRAWING: None

Description

The present invention relates to a method for producing a highly conductive composite, a method for producing an organic solvent dispersion of a highly conductive composite, a conductive film and a method for producing the same.

As a coating material for forming the conductive layer, a conductive polymer dispersion containing a conductive composite in which poly (3,4-ethylenedioxythiophene) is doped with polystyrene sulfonic acid may be used.
Patent Document 1 discloses a method of adding an epoxy compound to an anionic group of a conductive composite to make the conductive composite hydrophobic in order to improve the dispersibility of the conductive composite with respect to an organic solvent. There is.

JP-A-2019-8912

However, when the hydrophobized conductive composite is produced by the method of Patent Document 1, the desired reaction product produced in water may be separated by filtration. However, the time required for this filtration process is very long, and there is a problem that the filter paper is clogged, so that improvement in production efficiency has been required.
The present invention provides a method for producing a highly conductive composite having excellent production efficiency, a method for producing an organic solvent dispersion of a highly conductive composite, a conductive film and a method for producing the same.

[1] Obtaining a mixed solution of an aqueous dispersion of a conductive complex containing a π-conjugated conductive polymer and a polyanion and an organic solvent, and precipitating the highly conductive complex in the mixed solution. , And a method for producing a highly conductive composite, which comprises preparating the highly conductive composite to which the epoxy compound is added by adding an epoxy compound to the mixed solution.
[2] The method for producing a highly conductive composite according to [1], wherein the content of the organic solvent contained in the mixed solution is 50% by mass or more with respect to the total mass of the mixed solution.
[3] The method for producing a highly conductive composite according to [1] or [2], wherein the organic solvent contains at least one of a ketone solvent and an alcohol solvent.
[4] The method for producing a highly conductive composite according to [3], wherein the organic solvent contains a ketone solvent and the ketone solvent contains a methyl ethyl ketone.
[5] The method for producing a highly conductive composite according to [3], wherein the organic solvent contains an alcohol solvent and the alcohol solvent contains methanol.
[6] The method for producing a highly conductive composite according to [1] or [2], wherein the organic solvent contains methyl ethyl ketone and methanol.
[7] The highly conductive composite according to any one of [1] to [6], wherein the mixed solution is heated to 40 ° C. or higher when the highly conductive composite is precipitated in the mixed solution. Production method.
[8] When the highly conductive composite is precipitated in the mixed solution, the content of at least one of the acids and bases other than the polyanion in the mixed solution is 0 with respect to the total mass of the mixed solution. . The method for producing a highly conductive composite according to any one of [1] to [7], which is 1% by mass or less.
[9] The method for producing a highly conductive composite according to any one of [1] to [8], wherein the method for separating the highly conductive composite to which the epoxy compound is added is filtration.
[10] The method for producing a highly conductive composite according to any one of [1] to [9], wherein the π-conjugated conductive polymer is poly (3,4-ethylenedioxythiophene).
[11] The method for producing a highly conductive composite according to any one of [1] to [10], wherein the polyanion is polystyrene sulfonic acid.
[12] An organic solvent dispersion of a highly conductive composite, which comprises mixing a highly conductive composite obtained by the production method according to any one of [1] to [11] with an organic solvent. Manufacturing method.
[13] The method for producing an organic solvent dispersion of a highly conductive composite according to [12], which further comprises mixing a binder component.
[14] The method for producing an organic solvent dispersion of a highly conductive composite according to [13], wherein the binder component is a compound that forms an acrylic resin after curing.
[15] An organic solvent dispersion of a highly conductive composite obtained by the production method according to any one of [12] to [14] is applied to at least one surface of the film substrate to form the film. A method for producing a conductive film, which comprises drying a coating film.
[16] A conductive layer made of a cured layer of an organic solvent dispersion of a highly conductive composite obtained by the production method according to any one of [12] to [14] on at least one surface of the film substrate. Conductive film with.

According to the method for producing a highly conductive composite of the present invention, a highly conductive composite to which an epoxy compound is added can be easily obtained. Since the obtained highly conductive composite is hydrophobic, it can be easily dispersed in an organic solvent. When the highly conductive composite obtained by the present invention is used, it is possible to form a conductive layer having excellent conductivity as compared with the case where a conventional conductive composite is used.

≪Manufacturing method of highly conductive composite≫
In the first aspect of the present invention, a mixed solution obtained by mixing an aqueous dispersion of a conductive complex containing a π-conjugated conductive polymer and a polyanion and an organic solvent is obtained, and a highly conductive composite is contained in the mixed solution. A method for producing a highly conductive composite, which comprises precipitating a body and then adding an epoxy compound to the mixed solution to separate the highly conductive composite to which the epoxy compound is added. ..

[Aqueous dispersion of conductive composite]
The aqueous dispersion of the conductive composite used in this embodiment (hereinafter, may be referred to as “conductive polymer aqueous dispersion”) is a conductive composite containing a π-conjugated conductive polymer and a polyanion, and water. And contains. This aqueous dispersion may contain an organic solvent as long as the conductive composite in the liquid is in a dispersed state.

The polyanion is doped with a π-conjugated conductive polymer to form a conductive composite having conductivity. In the polyanion, only a part of the anion groups are doped in the π-conjugated conductive polymer, and the polyanion has a surplus anion group that does not participate in the doping. Since the excess anion group is a hydrophilic group, the conductive composite has dispersibility in water.

In the conductive polymer aqueous dispersion used in this embodiment, the conductive composite is in a dispersed state. The distinction between the dispersed state and the precipitated state can be easily visually performed. The transparency of the dispersed liquid is high, and no solid suspended matter is found in the dispersed liquid. On the other hand, the transparency of the precipitated liquid is low, and solid suspended matter is observed in the liquid. Normally, the conductive composite in a dispersed state does not easily precipitate, and even if it is allowed to stand for 12 hours, for example, precipitation is unlikely to occur. On the other hand, the suspended matter in the liquid in the precipitated state is likely to settle, and for example, by allowing it to stand for about 12 hours, precipitation is likely to occur.

When the conductive polymer aqueous dispersion used in this embodiment is passed through a filter having a reserved particle size of 7 μm, the dispersed conductive composite passes through the filter together with the dispersion medium. On the other hand, the conductive composite in the precipitated state can be captured by the filter.
Here, the reserved particle size of the filter paper is a guideline for the roughness of the mesh, and is obtained from the leaked particle size when barium sulfate or the like specified in JIS P 3801 [filter paper (for chemical analysis)] is naturally filtered.

(Π-conjugated conductive polymer)
The π-conjugated conductive polymer may be an organic polymer whose main chain is composed of a π-conjugated system. For example, a polypyrrole-based conductive polymer, a polythiophene-based conductive polymer, or a polyacetylene-based conductive polymer has high conductivity. Examples thereof include molecules, polyphenylene-based conductive polymers, polyphenylene vinylene-based conductive polymers, polyaniline-based conductive polymers, polyacene-based conductive polymers, polythiophene vinylene-based conductive polymers, and copolymers thereof. From the viewpoint of stability in air, polypyrrole-based conductive polymers, polythiophenes and polyaniline-based conductive polymers are preferable, and from the viewpoint of transparency, polythiophene-based conductive polymers are more preferable.

Examples of the polythiophene-based conductive polymer include polythiophene, poly (3-methylthiophene), poly (3-ethylthiophene), poly (3-propylthiophene), poly (3-butylthiophene), and poly (3-hexylthiophene). , Poly (3-heptylthiophene), Poly (3-octylthiophene), Poly (3-decylthiophene), Poly (3-dodecylthiophene), Poly (3-octadecylthiophene), Poly (3-bromothiophene), Poly (3-Chlorothiophene), poly (3-iodothiophene), poly (3-cyanothiophene), poly (3-phenylthiophene), poly (3,4-dimethylthiophene), poly (3,4-dibutylthiophene) , Poly (3-hydroxythiophene), Poly (3-methoxythiophene), Poly (3-ethoxythiophene), Poly (3-butoxythiophene), Poly (3-hexyloxythiophene), Poly (3-Heptyloxythiophene) , Poly (3-octyloxythiophene), Poly (3-decyloxythiophene), Poly (3-dodecyloxythiophene), Poly (3-octadecyloxythiophene), Poly (3,4-dihydroxythiophene), Poly (3) , 4-dimethoxythiophene), poly (3,4-diethoxythiophene), poly (3,4-dipropoxythiophene), poly (3,4-dibutoxythiophene), poly (3,4-dihexyloxythiophene) , Poly (3,4-diheptyloxythiophene), Poly (3,4-dioctyloxythiophene), Poly (3,4-didecyloxythiophene), Poly (3,4-didodecyloxythiophene), Poly ( 3,4-ethylenedioxythiophene), poly (3,4-propylenedioxythiophene), poly (3,4-butylenedioxythiophene), poly (3-methyl-4-methoxythiophene), poly (3- Methyl-4-ethoxythiophene), poly (3-carboxythiophene), poly (3-methyl-4-carboxythiophene), poly (3-methyl-4-carboxyethylthiophene), poly (3-methyl-4-carboxyphene) Butylthiophene).
Polypyrrole-based conductive polymers include polypyrrole, poly (N-methylpyrrole), poly (3-methylpyrrole), poly (3-ethylpyrrole), poly (3-n-propylpyrrole), and poly (3-butyl). Pyrrole), poly (3-octylpyrrole), poly (3-decylpyrrole), poly (3-dodecylpyrrole), poly (3,4-dimethylpyrrole), poly (3,4-dibutylpyrrole), poly (3) -Carboxypyrrole), poly (3-methyl-4-carboxypyrrole), poly (3-methyl-4-carboxyethylpyrrole), poly (3-methyl-4-carboxybutylpyrrole), poly (3-hydroxypyrrole) , Poly (3-methoxypyrrole), poly (3-ethoxypyrrole), poly (3-butoxypyrrole), poly (3-hexyloxypyrrole), poly (3-methyl-4-hexyloxypyrrole).
Examples of the polyaniline-based conductive polymer include polyaniline, poly (2-methylaniline), poly (3-isobutylaniline), poly (2-aniline sulfonic acid), and poly (3-aniline sulfonic acid).
Among these π-conjugated conductive polymers, poly (3,4-ethylenedioxythiophene) is particularly preferable from the viewpoint of conductivity, transparency, and heat resistance.
The π-conjugated conductive polymer contained in the conductive complex may be of one type or two or more types.

(Polyanion)
A polyanion is a polymer having two or more monomer units having an anion group in the molecule. The anionic group of this polyanion functions as a dopant for the π-conjugated conductive polymer and improves the conductivity of the π-conjugated conductive polymer.
The anion group of the polyanion is preferably a sulfo group or a carboxy group.
Specific examples of such polyanions include polystyrene sulfonic acid, polyvinyl sulfonic acid, polyallyl sulfonic acid, polyacrylic acid ester having a sulfo group, and polymethacrylic acid ester having a sulfo group (for example, poly (4-sulfobutyl methacrylate). , Polysulfoethyl methacrylate, polymethacryloyloxybenzenesulfonic acid), poly (2-acrylamide-2-methylpropanesulfonic acid), polyisoprenesulfonic acid and other polymers with sulfo groups, polyvinylcarboxylic acid, polystyrenecarboxylic acid, etc. Examples thereof include polymers having a carboxy group such as polyallyl carboxylic acid, polyacrylic acid, polymethacrylic acid, poly (2-acrylamide-2-methylpropanecarboxylic acid), and polyisoprenecarboxylic acid. The polyanion is a single monomer. It may be a homopolymer obtained by polymerizing the above, or it may be a copolymer obtained by polymerizing two or more kinds of monomers.
Among these polyanions, a polymer having a sulfo group is preferable, and polystyrene sulfonic acid is more preferable, because the conductivity can be made higher.
The polyanion may be used alone or in combination of two or more.
The mass average molecular weight of the polyanion is preferably 20,000 or more and 1 million or less, and more preferably 100,000 or more and 500,000 or less. The mass average molecular weight is a mass-based average molecular weight measured by gel permeation chromatography and determined in terms of polystyrene.

The content ratio of the polyanion in the conductive composite is preferably in the range of 1 part by mass or more and 1000 parts by mass or less with respect to 100 parts by mass of the π-conjugated conductive polymer, and is 10 parts by mass or more and 700 parts by mass or less. It is more preferable that the amount is 100 parts by mass or more and 500 parts by mass or less. When the content ratio of the polyanion is at least the above lower limit value, the doping effect on the π-conjugated conductive polymer tends to be strong, and the conductivity becomes higher. On the other hand, when the content of the polyanion is not more than the upper limit value, the π-conjugated conductive polymer can be sufficiently contained, so that sufficient conductivity can be ensured.

<Manufacturing method of conductive polymer aqueous dispersion>
A conductive polymer aqueous dispersion in which a conductive composite containing a π-conjugated conductive polymer and a polyanion is dispersed in an aqueous dispersion medium forms, for example, a π-conjugated conductive polymer in an aqueous solution of a polyanion. It can be obtained by chemically oxidizing and polymerizing a monomer. Further, a commercially available conductive polymer aqueous dispersion may be used.

The chemical oxidative polymerization can be carried out using a known catalyst and an oxidizing agent. Examples of the catalyst include transition metal compounds such as ferric chloride, ferric sulfate, ferric nitrate and cupric chloride. Examples of the oxidizing agent include persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate. The oxidant can restore the reduced catalyst to its original oxidized state.

The content of the conductive composite contained in the conductive polymer aqueous dispersion of this embodiment is preferably, for example, 0.1% by mass or more and 20% by mass or less with respect to the total mass of the aqueous dispersion. It is preferably 5% by mass or more and 10% by mass or less, and more preferably 1.0% by mass or more and 5.0% by mass or less.
When it is at least the lower limit of the above range, precipitation of the highly conductive composite after the addition of the organic solvent becomes easy. When it is not more than the upper limit of the above range, the dispersibility of the conductive composite in the conductive polymer aqueous dispersion is enhanced, so that unintentional aggregation during storage of the conductive polymer aqueous dispersion is prevented and an organic solvent is added. The quality of the highly conductive composite that is deposited later can be made uniform.

The conductive polymer aqueous dispersion used in this embodiment may contain an organic solvent as long as the conductive composite is in a dispersed state. The smaller the content of the organic solvent, the more preferable, and it is more preferable that the organic solvent is not substantially contained. The following is more preferable.
The organic solvent that may be contained in the conductive polymer aqueous dispersion used in this embodiment is preferably one having high miscibility with water, and examples thereof include alcoholic solvents described later.
In the present specification, the term "conductive polymer aqueous dispersion" is a term that clearly indicates that water is contained as a dispersion medium and no organic solvent is substantially contained.

[Preparation of mixed solution]
Examples of the method of mixing the conductive polymer aqueous dispersion and the organic solvent to obtain the mixed solution include a method of adding an organic solvent to the conductive polymer aqueous dispersion and a method of adding a conductive polymer aqueous dispersion to the organic solvent. Examples thereof include a method of adding a liquid. A preferred embodiment includes a method of gradually adding an organic solvent while stirring the conductive polymer aqueous dispersion. With this addition method, it is possible to prevent the concentration of the organic solvent in the conductive polymer aqueous dispersion from rising locally, and to gently precipitate the highly conductive composite. Sudden increases in organic solvent concentration can result in inhomogeneous aggregates of highly conductive composites.

The content of the organic solvent contained in the mixed solution is preferably 50% by mass or more and less than 100% by mass, more preferably 55% by mass or more and 90% by mass or less, and 60% by mass, based on the total mass of the mixed solution. More than 85% by mass is more preferable, and 60% by mass or more and 80% by mass or less is particularly preferable. Here, the content of the organic solvent is an amount containing the organic solvent contained in the conductive polymer aqueous dispersion before mixing.
When it is at least the lower limit of the above range, the precipitation of the highly conductive composite becomes easier, and the yield of the highly conductive composite is improved.
When it is not more than the upper limit of the above range, the conductive polymer aqueous dispersion contained in the mixed liquid can be relatively increased, so that the amount of the highly conductive composite to be sorted can be increased.

The appearance after mixing the conductive polymer aqueous dispersion and the organic solvent and allowing the obtained mixed solution to stand may be such that the water and the organic solvent are completely compatible with each other or separated from each other. Although it may be used, it is preferable that the highly conductive composite is sufficiently compatible from the viewpoint of facilitating the precipitation.

(Organic solvent)
As the organic solvent constituting the mixed solution of this embodiment, a water-soluble organic solvent is preferable. Here, the water-soluble organic solvent is an organic solvent having a dissolution amount of 1 g or more with respect to 100 g of water at a temperature of 20 ° C.
Examples of the water-soluble organic solvent include alcohol-based solvents, ketone-based solvents, and ester-based solvents.
Examples of the alcohol solvent include methanol, ethanol, isopropanol, n-butanol, t-butanol, allyl alcohol and the like.
Examples of the ketone solvent include methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl amyl ketone, diethyl ketone, diisopropyl ketone, acetone, diacetone alcohol and the like.
Examples of the ester solvent include methyl acetate, ethyl acetate, propyl acetate, butyl acetate and the like.
One type of organic solvent may be used alone, or two or more types may be used in combination.

The organic solvent constituting the mixed solution of this embodiment preferably contains at least one of a ketone solvent and an alcohol solvent.
It is preferable to contain methyl ethyl ketone as the ketone solvent.
As the alcohol solvent, methanol or isopropanol is preferable.
When the above-mentioned suitable organic solvent is contained, the highly conductive composite can be more easily precipitated in the mixed solution, and the yield can be further improved.

In the mixed solution of this embodiment, methyl ethyl ketone is preferably contained in combination with methanol or isopropanol, and more preferably in combination with methanol. In this case, the content of methanol or isopropanol with respect to 100 parts by mass of methyl ethyl ketone is preferably 1 part by mass or more and 100 parts by mass or less, more preferably 3 parts by mass or more and 50 parts by mass or less, and further preferably 6 parts by mass or more and 20 parts by mass or less. ..
When the above-mentioned suitable combination of organic solvents is contained, the highly conductive composite can be more easily precipitated in the mixed solution, and the yield can be further improved.
When the organic solvent is contained in the above-mentioned suitable range, the highly conductive composite can be more easily precipitated in the mixed solution, and the yield can be further improved.

In the mixed solution of this embodiment, isopropanol is preferably contained in combination with methyl acetate or ethyl acetate. In this case, the content of methyl acetate or ethyl acetate with respect to 100 parts by mass of isopropanol is preferably 10 parts by mass or more and 300 parts by mass or less, more preferably 30 parts by mass or more and 200 parts by mass or less, and 60 parts by mass or more and 100 parts by mass or less. More preferred.
When the above-mentioned suitable combination of organic solvents is contained, the highly conductive composite can be more easily precipitated in the mixed solution, and the yield can be further improved.
When the organic solvent is contained in the above-mentioned suitable range, the highly conductive composite can be more easily precipitated in the mixed solution, and the yield can be further improved.

In the mixed solution of this embodiment, it is preferable that methyl ethyl ketone, isopropanol, and methyl acetate or ethyl acetate are contained in combination. In this case, the content of methyl acetate or ethyl acetate with respect to 100 parts by mass of isopropanol is preferably 10 parts by mass or more and 300 parts by mass or less, more preferably 30 parts by mass or more and 200 parts by mass or less, and 60 parts by mass or more and 100 parts by mass or less. More preferred. The content of methyl ethyl ketone with respect to 100 parts by mass of isopropanol is preferably 100 parts by mass or more and 3000 parts by mass or less, more preferably 200 parts by mass or more and 2000 parts by mass or less, and further preferably 500 parts by mass or more and 1000 parts by mass or less.
When the above-mentioned suitable combination of organic solvents is contained, the highly conductive composite can be more easily precipitated in the mixed solution, and the yield can be further improved.
When the organic solvent is contained in the above-mentioned suitable range, the highly conductive composite can be more easily precipitated in the mixed solution, and the yield can be further improved.

When the highly conductive composite is precipitated in the mixed solution of this embodiment, the content of at least one of the acids and bases other than the polyanion in the mixed solution is 0.1 with respect to the total mass of the mixed solution. It is preferably 1% by mass or less, more preferably 0.01% by mass or less, and most preferably not substantially contained.
Examples of the acid include inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as paratoluene sulfonic acid and naphthalene sulfonic acid.
Examples of the base include inorganic bases such as sodium hydroxide and sodium carbonate, and organic bases such as trioctylamine and octylamine.
The above acids and bases can be a cause of inhibiting the precipitation of highly conductive complexes in the mixed solution of this embodiment.

[Precipitation of highly conductive composite]
The method for precipitating the highly conductive composite in the prepared mixed solution is not particularly limited, and the mixed solution can be precipitated even by allowing the mixed solution to stand. Further, it is not necessary to allow the mixture to stand completely, and the precipitate may be precipitated with gentle stirring.

When precipitating the highly conductive composite in the mixed solution, it is preferable to heat the mixed solution. The heating temperature is preferably 40 ° C. or higher, more preferably 50 ° C. or higher and 100 ° C. or lower, and even more preferably 60 ° C. or higher and 80 ° C. or lower. The heating time at the above-mentioned suitable heating temperature can be, for example, 1 hour or more and 10 hours or less.
When the mixed solution is heated, the highly conductive composite can be easily precipitated in the mixed solution, and the yield of the highly conductive composite can be improved.

[Addition of epoxy compound]
By adding an epoxy compound to the mixed solution in which the above-mentioned highly conductive composite is precipitated, the epoxy compound is added to some anionic groups of the polyanions constituting the highly conductive composite, and the highly conductive composite is formed. It can be made hydrophobic. The highly conductive composite before hydrophobization has high dispersibility in water, and the hydrophobized highly conductive composite has high dispersibility in organic solvents.
The structure of the substituent in which the epoxy compound is added to the surplus anion group not involved in the doping of the polyanion is a substitution represented by the following chemical formula (A1) or the following chemical formula (A2) formed by the ring opening reaction of the epoxy group. It is considered to be the group (A).

［式（Ａ１）中、Ｒ^１１、Ｒ^１２、Ｒ^１３、及びＲ^１４はそれぞれ独立に、水素原子、又は任意の置換基である。］

[In formula (A1), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently a hydrogen atom or an arbitrary substituent. ]

［式（Ａ２）中、ｍは２以上の整数であり、複数のＲ^１５、複数のＲ^１６、複数のＲ^１７、及び複数のＲ^１８はそれぞれ独立に、水素原子、又は任意の置換基であり、複数のＲ^１５は同一でも異なっていてもよく、複数のＲ^１６は同一でも異なっていてもよく、複数のＲ^１７は同一でも異なっていてもよく、複数のＲ^１８は同一でも異なっていてもよい。］

[In formula (A2), m is an integer of 2 or more, and the plurality of R ¹⁵ , the plurality of R ¹⁶ , the plurality of R ¹⁷ , and the plurality of R ¹⁸ are independently hydrogen atoms or arbitrary substituents. Yes, a plurality of R ^15s may be the same or different, a plurality of R ^16s may be the same or different, a plurality of R ^17s may be the same or different, and a plurality of R ^18s may be the same or different. You may. ]

In the formulas (A1) and (A2), the leftmost bond represents that the substituent (A) is substituted with the proton of the anion group. Examples of the anion group having a proton to be substituted include an anion group having an active proton bonded to an oxygen atom such as " _{-SO 3 H".}

In the formula (A1), ^{as arbitrary substituents of R 11} , R ¹² , R ¹³ and R ¹⁴ , an aliphatic hydrocarbon group having 1 to 20 carbon atoms and a substituent which may have a substituent are used. Examples thereof include aromatic hydrocarbon groups having 6 to 20 carbon atoms which may be possessed. R ¹¹ and R ¹³ may be bonded to each other to form a ring which may have a substituent. For example, R ¹¹ and R ¹³ are the hydrocarbon groups, and a divalent hydrocarbon group excluding any one hydrogen atom of the monovalent hydrocarbon group of ^{R 11 and a monovalent hydrocarbon of R 13} are used. A case may be mentioned in which a divalent hydrocarbon group excluding any one hydrogen atom of a hydrogen group is bonded to each other by carbon atoms from which the hydrogen atom has been removed to form a ring.

In the present specification, "may have a substituent" means that the hydrogen atom (-H) is replaced with a monovalent group and the methylene group (-CH _2- ) is replaced with a divalent group. Includes both cases of replacement.
The monovalent group as a substituent includes an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), and a trialkoxysilyl group. (Trimethoxysilyl group, etc.), and the like.
Examples of the divalent group as the substituent include an oxygen atom (-O-), -C (= O)-, -C (= O) -O- and the like. However, this does not apply when two oxygen atoms are adjacent to each other.

In the formula (A2), ^{as arbitrary substituents of R 15} , R ¹⁶ , R ¹⁷ , and R ¹⁸ , an aliphatic hydrocarbon group having 1 to 20 carbon atoms, which may have a substituent, and a substituent are used. Examples thereof include aromatic hydrocarbon groups having 6 to 20 carbon atoms which may be possessed. R15 and R17 may be bonded to form a ring which may have a substituent. The example of forming a ring is the same as described above.

In the formula (A2), m is an integer of 2 or more, preferably 2 to 100, more preferably 2 to 50, and even more preferably 2 to 25. When m is not more than the above lower limit value, the hydrophobicity of the highly conductive composite becomes sufficiently high. When m is not more than the upper limit value, it is possible to prevent the hydrophobicity from becoming too high and the conductivity from being lowered.

In this embodiment, the highly conductive composite is in a pre-precipitated state in the mixed solution before the epoxy compound is added. Therefore, the epoxy compound may have a smaller number of carbon atoms than before.
Conventionally, as disclosed in Patent Document 1, an epoxy compound is added to a conductive composite uniformly dispersed in water, and the adduct is precipitated in water. In order to precipitate the hydrophilic conductive complex in water, it was necessary to form a substituent (A) having a large number of carbon atoms and high hydrophobicity. Specifically, a higher alcohol glycidyl ether mixed with 12 or 13 carbon atoms was added to form a substituent (A) having 12 or more carbon atoms. When the substituent (A) has a small number of carbon atoms, it does not precipitate, or even if it barely precipitates, the filter paper is often clogged when it is separated by filtration, and it may take a lot of time and effort to separate it. there were.
On the other hand, in this embodiment, since the highly conductive composite is precipitated in advance, it is sufficient to add an epoxy compound having a small number of carbon atoms to neutralize the charge of the excess anion group. From this viewpoint, the number of carbon atoms of the substituent (A) is preferably 1 to 10, more preferably 2 to 8, and even more preferably 2 to 6. When it is equal to or higher than the lower limit of the carbon number range, the highly conductive composite becomes sufficiently hydrophobic, can be easily separated from the mixed solution, and the separated highly conductive composite has dispersibility in an organic solvent. Is improved. When it is not more than the upper limit of the above carbon number range, the bulkiness of the substituent (A) is reduced, it is not easily affected by the steric hindrance of the substituent (A), and the highly conductive composite exhibits high conductivity. can do.

The molecular weight of the epoxy compound added to the mixed solution is, for example, preferably 50 or more and 1000 or less, more preferably 60 or more and 300 or less, and further preferably 70 or more and 200 or less.
Within the above range, the above-mentioned suitable substituent (A) can be formed.

The epoxy compound is a compound having one or more epoxy groups in one molecule.
One type of epoxy compound may be used alone, or two or more types may be used in combination.

Examples of the monofunctional epoxy compound having one epoxy group in one molecule include ethylene oxide, propylene oxide, 2,3-butylene oxide, isobutylene oxide, 1,2-butylene oxide, 1,2-epoxyhexane, and 1 , 2-Epoxy heptane, 1,2-epoxypentane, 1,2-epoxy octane, 1,2-epoxydecane, 1,3-butadiene monooxide, 1,2-epoxytetradecane, glycidyl methyl ether, 1,2- Epoxy octadecane, 1,2-epoxyhexadecan, ethyl glycidyl ether, glycidyl isopropyl ether, tert-butyl glycidyl ether, 1,2-epoxyeicosan, 2- (chloromethyl) -1,2-epoxypropane, glycidol, epichlorohydrin, Epibromohydrin, butyl glycidyl ether, 1,2-epoxyhexane, 1,2-epoxy-9-decane, 2- (chloromethyl) -1,2-epoxybutane, 2-ethylhexyl glycidyl ether, 1,2- Epoxy-1H, 1H, 2H, 2H, 3H, 3H-trifluorobutane, allyl glycidyl ether, tetracyanoethylene oxide, glycidyl butyrate, 1,2-epoxycyclooctane, glycidyl methacrylate, 1,2-epoxycyclododecane, 1-Methyl-1,2-epoxycyclohexane, 1,2-epoxycyclopentadecane, 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, 1,2-epoxy-1H, 1H, 2H, 2H, 3H, 3H-Heptadecafluorobutane, 3,4-epoxy tetrahydrofuran, glycidyl stearate, 3-glycidyloxypropyltrimethoxysilane, epoxysuccinic acid, glycidylphenyl ether, isophorone oxide, α-pinene oxide, 2,3-epoxynorbornene, Benzyl glycidyl ether, diethoxy (3-glycidyloxypropyl) methylsilane, 3- [2- (perfluorohexyl) ethoxy] -1,2-epoxypropane, 1,1,1,3,5,5,5-heptamethyl- 3- (3-glycidyloxypropyl) trisiloxane, 9,10-epoxy-1,5-cyclododecadien, 4-tert-butyl glycidyl benzoate, 2,2-bis (4-glycidyloxyphenyl) propane, 2 -Ether-butyl-2- [2- (4-chlorophenyl) )] Ethyloxylan, styrene oxide, glycidyl trityl ether, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2-phenylpropylene oxide, cholesterol-5α, 6α-epoxide, stillbenoxide, glycidyl p-toluenesulfonate , 3-Methyl-3-phenylglycidate, N-propyl-N- (2,3-epoxypropyl) perfluoro-n-octylsulfonamide, (2S, 3S) -1,2-epoxide-3-( tert-Butoxycarbonylamino) -4-phenylbutane, 3-nitrobenzene sulfonic acid (R) -glycidyl, 3-nitrobenzene sulfonic acid-glycidyl, parthenolide, N-glycidyl phthalimide, endolin, dildoline, 4-glycidyl oxycarbazole, 7, Examples thereof include 7-dimethyloctanoic acid [oxylanylmethyl], 1,2-epoxide-4-vinylcyclohexane, higher alcohol glycidyl ether having 10 to 16 carbon atoms, diallyl monoglycidyl isocyanurate and the like.

Examples of the polyfunctional epoxy compound having two or more epoxy groups in one molecule include 1,6-hexanediol diglycidyl ether, 1,7-octadiene epoxide, neopentyl glycol diglycidyl ether, and 4-butanediol. Diglycidyl ether, 1,2: 3,4-diepoxide butane, 1,2-cyclohexanedicarboxylic acid diglycidyl, triglycidyl isocyanurate, neopentyl glycol diglycidyl ether, 1,2: 3,4-diepoxide butane, polyethylene Glycol diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, Trimethylol propane triglycidyl ether, trimethylol propane polyglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hexahydrophthalic acid diglycidyl ether, glycerin polyglycidyl ether, diglycerin polyglycidyl ether, polyglycerin polyglycidyl ether, sorbitol poly Examples thereof include glycidyl ether and ethylene oxide lauryl alcohol glycidyl ether.

The amount of the epoxy compound added to the mixed solution shall be 1 part by mass or more and 10000 parts by mass or less with respect to 100 parts by mass of the total mass of the π-conjugated conductive polymer and the polyanion contained in the mixed solution. It is more preferably 100 parts by mass or more and 5000 parts by mass or less, further preferably 200 parts by mass or more and 1000 parts by mass or less, and particularly preferably 300 parts by mass or more and 800 parts by mass or less. When the addition ratio of the epoxy compound is at least the above lower limit value, the dispersibility of the highly conductive composite with respect to the organic solvent becomes higher, and when it is at least the above upper limit value, the decrease in conductivity of the highly conductive composite is prevented. be able to.

[Separation of highly conductive composite]
The method for separating (recovering) the highly conductive composite to which the epoxy compound is added in the mixed solution is not particularly limited, and for example, filtration, decantation, centrifugation, vacuum drying, freeze drying, spray drying. And so on.
Of these, filtration or decantation is preferable because it is easy to separate the components other than the highly conductive composite contained in the mixed solution from the highly conductive composite. Here, the filtration is an operation of capturing the highly conductive composite in a filter through which the mixed solution has passed. Further, decantation is an operation of precipitating the precipitated highly conductive composite and removing the supernatant liquid.
When sorting by filtration, it is necessary to deal with clogging of the filter. Further, since the solid substance of the highly conductive composite is compressed on the filter by the filtration pressure, the highly conductive composite separated by filtration tends to be in a harder state than when separated by decantation. Since the highly conductive composite obtained by decantation is obtained in a relatively soft powder state, it can be easily dispersed later in a dispersion medium.
On the other hand, in the case of decantation, it is necessary to wait until the highly conductive composite precipitates in the mixed solution. From the viewpoint of increasing the production speed of the highly conductive composite, it is preferable to separate by filtration.

The separated highly conductive composite is preferably washed with an organic solvent in which the highly conductive composite is difficult to dissolve. Specifically, for example, the organic solvent may be poured over the filter that captures the highly conductive composite, or the organic solvent is added to the highly conductive composite remaining at the bottom of the container after decantation and stirred. After that, it may be sorted again by decantation or the like.
A dried body of the highly conductive composite can be obtained by drying and removing the organic solvent or the like adhering to the separated highly conductive composite.

<Effect>
According to the method for producing a highly conductive composite of the present invention, almost all of the conductive composite contained in the mixed solution is recovered as a precipitate of an adduct (reactant) of the highly conductive composite with an epoxy compound. can do. That is, the method for producing a highly conductive composite of this embodiment can exhibit a high yield of 90 to 100% by mass. In addition, it is extremely easy to separate the precipitates by filtration. The reason for this is considered to be that the size of the precipitate is larger than before and it is difficult to clog the filter paper.
In the method for producing a highly conductive composite of the present invention, it is presumed that the reason why the highly conductive composite is precipitated in the mixed solution containing an organic solvent is that the highly conductive composite is difficult to dissolve in the organic solvent. To.
Surprisingly, when the highly conductive composite precipitated in the production method of the present invention is used, an epoxy compound is added to a conventional conductive composite (for example, a non-precipitated conductive composite in a dispersed state). It is possible to form a conductive layer having more excellent conductivity than the case of using the obtained hydrophobic conductive composite) (see Examples and Comparative Examples described later). The difference in chemical composition between the highly conductive composite after precipitation and the conventional conductive composite is considered to be the presence or absence of a very small amount of organic solvent adhering to the highly conductive composite at the molecular level, if any. Be done. It is considered that the difference in physicochemical properties rather than the chemical composition influences the difference in conductivity.

<< Manufacturing method of organic solvent dispersion of highly conductive composite >>
The second aspect of the present invention is a method for producing an organic solvent dispersion of a highly conductive composite, which comprises mixing the highly conductive composite obtained by the production method of the first aspect with an organic solvent. ..
Since the epoxy compound is added to the highly conductive composite obtained in the first aspect, the dispersibility in an organic solvent is high.

(Organic solvent)
The organic solvent used in the production method of this embodiment can be said to be a dispersion medium or a solvent because it can disperse or dissolve a highly conductive composite. In the present specification, dispersion and dissolution may be simply referred to as dispersion without distinction, and dispersion medium and solvent may be simply referred to as dispersion medium without distinction.
Specific examples of the organic solvent include hydrocarbon solvents, ketone solvents, alcohol solvents, ester solvents, nitrogen atom-containing compound solvents and the like. One type of organic solvent may be used alone, or two or more types may be used in combination.
Examples of the hydrocarbon solvent include an aliphatic hydrocarbon solvent and an aromatic hydrocarbon solvent. Examples of the aliphatic hydrocarbon solvent include pentane, hexane, heptane, octane, decane, cyclohexane, methylcyclohexane and the like. Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, ethylbenzene, propylbenzene, isopropylbenzene and the like.
Examples of the ketone solvent include diethyl ketone, methyl propyl ketone, methyl butyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl amyl ketone, diisopropyl ketone, methyl ethyl ketone, acetone, diacetone alcohol and the like.
Examples of the alcohol solvent include methanol, ethanol, isopropanol, n-butanol, t-butanol, allyl alcohol and the like.
Examples of the ester solvent include ethyl acetate, propyl acetate, butyl acetate and the like.
Examples of the nitrogen atom-containing compound solvent include N-methylpyrrolidone, dimethylacetamide, dimethylformamide and the like.

Among the above organic solvents, alcohol-based solvents have high wettability of the highly conductive composite organic solvent dispersion with respect to the plastic film base material, and can easily solubilize relatively highly polar binder components. Is preferable. Further, among the alcohol solvents, isopropanol is preferable because the highly conductive composite to which the epoxy compound is added has good dispersibility.

The content ratio of the organic solvent is preferably 50% by mass or more and 99.5% by mass or less, and more preferably 70% by mass or more and 99% by mass or less, based on the total mass of the organic solvent dispersion liquid of the highly conductive composite. When the content ratio of the organic solvent is within the above range, the dispersibility of the highly conductive composite can be enhanced.

In this embodiment, the method of mixing the highly conductive composite and the organic solvent is not particularly limited. When an organic solvent is mixed with the highly conductive composite, the hydrophobized highly conductive composite is easily dispersed. The mixed solution may be subsequently stirred for further dispersion treatment. The stirring method is not particularly limited, and stirring may be performed with a weak shearing force such as a stirrer, or may be stirred using a disperser having a high shearing force (high pressure homogenizer or the like).

The particle size distribution of the highly conductive composite dispersed in the organic solvent dispersion obtained by the production method of this embodiment is not particularly limited, but is preferably 300 nm or less, more preferably 250 nm or less, and more preferably 200 nm or less. Is more preferable. Since the highly conductive composite contains a polymer, the lower limit is 1 nm or more as a guide, considering the molecular radius of the polymer.
The smaller the particle size distribution, the better the conductivity of the conductive layer formed by applying the organic solvent dispersion of the highly conductive composite of this embodiment.
Here, the particle size distribution is a value obtained by measuring the average particle size of cumulant by a dynamic light scattering method.

The content of the highly conductive composite with respect to the total mass of the organic solvent dispersion liquid of the highly conductive composite of this embodiment is, for example, preferably 0.01% by mass or more and 10% by mass or less, and 0.1% by mass or more. 5% by mass or less is more preferable, and 0.2% by mass or more and 1.0% by mass or less is further preferable.
Within the above range, the highly conductive composite can be dispersed more stably.

(Binder component)
The organic solvent dispersion of the highly conductive composite of this embodiment may contain a binder component. The binder component is a resin other than the π-conjugated conductive polymer and the polyanion or a precursor thereof, and is a thermoplastic resin or a curable monomer or oligomer that cures when a conductive layer (conductive film) is formed. The thermoplastic resin becomes a binder resin as it is, and the curable monomer or oligomer is a binder resin formed by curing.
One type of binder component may be used alone, or two or more types may be used in combination.

The curable monomer or oligomer may be a thermosetting monomer or oligomer, or may be a photocurable monomer or oligomer. Here, the oligomer is a polymer having a mass average molecular weight of less than 10,000.
Examples of the curable monomer include an acrylic monomer (acrylic compound) and an epoxy monomer. Examples of the curable oligomer include an acrylic oligomer (acrylic compound) and an epoxy oligomer.
When an acrylic monomer or an acrylic oligomer is used as the binder component, it can be easily cured by heating or light irradiation.

When a curable monomer or oligomer is contained, it is preferable to further contain a curing catalyst. For example, when a thermosetting monomer or oligomer is contained, it is preferable to contain a thermosetting initiator that generates radicals by heating, and when a photocurable monomer or oligomer is contained, radicals are generated by light irradiation. It is preferable to include a photopolymerization initiator to be allowed to be used.

Specific examples of the binder resin derived from the binder component include acrylic resin (acrylic compound), polyester resin, polyurethane resin, polyimide resin, polyether resin, melamine resin, polyacrylamide resin, silicone and the like.
The binder resin contained in the organic solvent dispersion of the highly conductive composite of this embodiment has good dispersibility in an organic solvent, and therefore forms a compound that forms an acrylic resin after curing and a polyacrylamide resin after curing. Compounds are preferred. The acrylic resin preferably contains an acrylic resin having a urethane bond in its molecular structure.

The content ratio of the binder component in the organic solvent dispersion of the highly conductive composite of this embodiment is preferably 100 parts by mass or more and 50,000 parts by mass or less, and 1000 parts by mass with respect to 100 parts by mass of the highly conductive composite. More preferably, it is 20000 parts by mass or less. When the content ratio of the binder component is at least the above lower limit value, the film forming property and the film strength when the organic solvent dispersion liquid of the highly conductive composite of this embodiment is applied to the film substrate can be improved. When the content ratio of the binder component is not more than the upper limit value, it is possible to suppress the decrease in conductivity due to the decrease in the content ratio of the highly conductive composite.

(Other additives)
The organic solvent dispersion of the highly conductive composite described above may contain other additives.
The additive is not particularly limited as long as the effect of the present invention can be obtained, and examples thereof include a surfactant, an inorganic conductive agent, a defoaming agent, a coupling agent, an antioxidant, and an ultraviolet absorber. However, the additive is other than the π-conjugated conductive polymer, the polyanion, the organic solvent, and the binder component.
Examples of the surfactant include nonionic, anionic and cationic surfactants, and nonionic surfactants are preferable from the viewpoint of storage stability. Further, a polymer-based surfactant such as polyvinylpyrrolidone may be added.
Examples of the inorganic conductive agent include metal ions and conductive carbon. The metal ion can be generated by dissolving the metal salt in water.
Examples of the defoaming agent include silicone resin, polydimethylsiloxane, silicone oil and the like.
Examples of the coupling agent include a silane coupling agent having a vinyl group or an amino group.
Examples of UV absorbers include benzotriazole-based UV absorbers, benzophenone-based UV absorbers, salicylate-based UV absorbers, cyanoacrylate-based UV absorbers, oxanilide-based UV absorbers, hindered amine-based UV absorbers, benzoate-based UV absorbers, etc. Can be mentioned.
When the organic solvent dispersion liquid of the above-mentioned highly conductive composite contains the above-mentioned additive, the content ratio thereof is appropriately determined according to the type of the additive, and is, for example, with respect to 100 parts by mass of the highly conductive composite. Therefore, the range can be 0.001 part by mass or more and 5 parts by mass or less.

<Effect>
The organic solvent dispersion of the highly conductive composite obtained by the production method of the present invention has excellent dispersibility of the highly conductive composite, and the highly conductive composite in the conductive layer formed from the organic solvent dispersion. Excellent dispersibility. Therefore, the conductivity of the conductive layer can be sufficiently increased. Further, since the highly conductive composite has good dispersibility, the storage stability of the above-mentioned organic solvent dispersion is also excellent.

≪Manufacturing method of conductive film≫
In the third aspect of the present invention, the organic solvent dispersion of the highly conductive composite obtained by the production method of the second aspect is applied to at least one surface of the film substrate, and the formed coating film is dried. It is a method for producing a conductive film including the above.

Examples of the film base material used in this embodiment include a plastic film.
Examples of the resin for the film base material constituting the plastic film include ethylene-methylmethacrylate copolymer resin, ethylene-vinyl acetate copolymer resin, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinyl alcohol, polyethylene terephthalate, and polybutylene terephthalate. , Polyethylene naphthalate, polyacrylate, polycarbonate, polyvinylidene fluoride, polyarylate, styrene-based elastomer, polyester-based elastomer, polyether sulfone, polyetherimide, polyether ether ketone, polyphenylene sulfide, polyimide, cellulose triacetate, cellulose acetate propio Examples include Nate. Among these resins for film substrates, polyethylene terephthalate is preferable because it is inexpensive and has excellent mechanical strength.
The resin for a film base material may be amorphous or crystalline.
Further, the film base material may be unstretched or stretched.
Further, the film base material may be subjected to surface treatment such as corona discharge treatment, plasma treatment, flame treatment, etc. in order to further improve the adhesion of the conductive layer to be formed.

The average thickness of the film substrate is preferably 10 μm or more and 500 μm or less, and more preferably 20 μm or more and 200 μm or less. If the average thickness of the film substrate is at least the lower limit value, it is difficult to break, and if it is at least the upper limit value, sufficient flexibility as a film can be ensured.
The thickness of the member in the present specification is a value obtained by measuring the thickness at an arbitrary 10 points and averaging the measured values.

(Coating process)
Examples of the method of applying the organic solvent dispersion of a highly conductive composite to a film substrate include a gravure coater, a roll coater, a curtain flow coater, a spin coater, a bar coater, a reverse coater, a kiss coater, a fountain coater, and a rod coater. , Coating method using coaters such as air doctor coater, knife coater, blade coater, cast coater, screen coater, spraying method using sprayer such as air spray, airless spray, rotor dampening, dipping method such as dip, etc. Can be applied.
Of the above, a bar coater may be used because it can be easily applied. In the bar coater, the coating thickness differs depending on the type, and in the commercially available bar coater, a number is assigned to each type, and the larger the number, the thicker the coating can be applied.
The amount of the dispersion liquid applied to the film substrate is not particularly limited, but the solid content should be in the range of ^{0.1 g / m 2} or more and 10.0 g / m ^{2 or less from the viewpoint of obtaining good conductivity.} Is preferable.

(Drying process)
Examples of the method for drying the coating film formed on the film substrate include heat drying and vacuum drying. As the heat drying, for example, a usual method such as hot air heating or infrared heating can be adopted. When heat drying is applied, the heating temperature is appropriately set according to the dispersion medium used, and can be set to, for example, 50 ° C. or higher and 150 ° C. or lower. Here, the heating temperature is a set temperature of the drying device. The drying time when drying at the above temperature can be, for example, 30 seconds or more and 3 minutes or less.
When the coating film contains an active energy ray-curable binder component, it may further have an active energy ray irradiation step of irradiating the dried coating film with active energy rays. When the active energy ray irradiation step is provided, the formation speed of the conductive layer can be increased, and the productivity of the conductive film is improved.
Examples of the active energy ray include ultraviolet rays, electron beams, visible rays and the like. As the light source of ultraviolet rays, for example, a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, or a metal halide lamp can be used.
The illuminance in ultraviolet irradiation is preferably ^{100 mW / cm 2} or more from the viewpoint of sufficiently curing the conductive layer. Further, from the viewpoint of sufficiently curing the conductive layer, the integrated light intensity is ^{preferably 50 mJ / cm 2} or more. In addition, the illuminance and the integrated light amount in this specification use UVR-T1 (industrial UV checker, receiver; UD-T36, measurement wavelength range; 300 nm or more and 390 nm or less, peak sensitivity wavelength; about 355 nm) manufactured by Topcon. It is a measured value.

≪Conductive film≫
In the fourth aspect of the present invention, a conductive layer made of a cured layer of an organic solvent dispersion of a highly conductive composite obtained by the production method of the second aspect is provided on at least one surface of the film substrate. It is a film. The conductive film of this aspect can be produced by the production method of the third aspect.

The conductive film obtained by this aspect includes a film base material and a conductive layer formed on at least one surface of the film base material. The conductive layer contains the highly conductive composite of the first aspect. An epoxy compound is added to some of the anion groups of some of the polyanions contained in the conductive layer.
When the applied organic solvent dispersion liquid contains a binder component, the conductive layer contains a binder component or a cured product obtained by curing the binder component.

The average thickness of the conductive layer of the conductive film of this embodiment is preferably, for example, 10 nm or more and 50,000 nm or less, and more preferably 20 nm or more and 40,000 nm or less. If the average thickness of the conductive layer is at least the lower limit value, sufficiently high conductivity can be exhibited, and if it is at least the upper limit value, the conductive layer can be easily formed.

The surface resistance of the conductive layer of the conductive film of the present embodiment, as an indication of good conductivity, for example, is preferably 1 × 10 ² Ω / □ or more 1 × 10 ⁸ Ω / □ or less, 1 × 10 ³ Ω / □ or more and 1 × 10 ⁷ Ω / □ or less are more preferable, and 1 × 10 ⁴ Ω / □ or more and 1 × 10 ⁶ Ω / □ or less are further preferable.

<Effect>
Since the conductive layer of the conductive film of the fourth aspect of the present invention contains a highly conductive composite, it is more conductive than the conventional conductive layer containing the conductive composite.

(Production Example 1) Synthesis of polystyrene sulfonic acid 1.14 g of ammonium persulfate oxidant solution previously dissolved in 10 ml of water was added by dissolving 206 g of sodium styrene sulfonate in 1000 ml of ion-exchanged water and stirring at 80 ° C. The solution was added dropwise for 20 minutes and the solution was stirred for 12 hours.
1000 ml of sulfuric acid diluted to 10% by mass was added to the obtained sodium polystyrene sulfonate-containing solution, and about 1000 ml of the solvent of the polystyrene sulfonate-containing solution was removed by an ultrafiltration method. Next, 2000 ml of ion-exchanged water was added to the residual liquid, about 2000 ml of the solvent was removed by an ultrafiltration method, and polystyrene sulfonic acid was washed with water. This washing operation was repeated 3 times.
Water in the obtained solution was removed under reduced pressure to obtain a colorless solid polystyrene sulfonic acid.

(Production Example 2) Synthesis of conductive polymer aqueous dispersion 14.2 g of 3,4-ethylenedioxythiophene and 36.7 g of polystyrene sulfonic acid dissolved in 2000 ml of ion-exchanged water are mixed at 20 ° C. I let you.
The mixed solution thus obtained was kept at 20 ° C., and while stirring, 29.64 g of ammonium persulfate dissolved in 200 ml of ion-exchanged water and 8.0 g of a ferric sulfate oxidation catalyst solution were slowly added. The reaction was carried out with stirring for 3 hours.
2000 ml of ion-exchanged water was added to the obtained reaction solution, and about 2000 ml of the solvent was removed by an ultrafiltration method. This operation was repeated 3 times.
Then, 200 ml of sulfuric acid diluted to 10% by mass and 2000 ml of ion-exchanged water were added to the obtained solution, and about 2000 ml of the solvent was removed by an ultrafiltration method. 2000 ml of ion-exchanged water was added to the residual liquid, and about 2000 ml of the solvent was removed by an ultrafiltration method. This operation was repeated 3 times.
Further, 2000 ml of ion-exchanged water was added to the obtained solution, and about 2000 ml of the solvent was removed by an ultrafiltration method. This operation was repeated 5 times to obtain a 1.2% polystyrene sulfonate-doped poly (3,4-ethylenedioxythiophene) (PEDOT-PSS aqueous dispersion) solution.

(Example 1)
A mixed solution prepared by adding 15.0 g of methanol and 200 g of methyl ethyl ketone to 100 g (solid content 1.2 g) of the PEDOT-PSS aqueous dispersion of Production Example 2 was heated and stirred at 60 ° C. for 3 hours. Next, when the mixed solution was returned to room temperature (20 to 25 ° C.) and allowed to stand for 1 hour, the highly conductive composite composed of PEDOT-PSS precipitated in the mixed solution was precipitated, and the upper layer (supernatant) was formed. It became a transparent liquid.
Next, 5.0 g of 1,2-butylene oxide (hereinafter, abbreviated as butylene oxide) was added to the mixed solution and stirred for 1 hour to add butylene oxide to the precipitate of the highly conductive complex. ..
Subsequently, by filtration, 2.3 g of a highly conductive composite to which the epoxy compound was added was obtained. The separation of the highly conductive composite by this filtration treatment was completed in 5 minutes or less.
The highly conductive composite collected by filtration was washed with 100 g of acetone and dried. 472.7 g of isopropanol was added to 2.3 g of this highly conductive composite and dispersed with a high-pressure homogenizer to obtain an isopropanol dispersion of the highly conductive composite. Next, a part of the above isopropanol dispersion was applied onto a PET film (Lumilar T60 manufactured by Toray Industries, Inc.) using a # 14 bar coater, and dried at 150 ° C. for 1 minute to obtain a conductive film. Table 1 shows the results of measuring the surface resistance value of the obtained conductive film.

(Example 2)
A mixed solution prepared by adding 15.0 g of methanol and 200 g of methyl ethyl ketone to 100 g (solid content 1.2 g) of the PEDOT-PSS aqueous dispersion of Production Example 2 was heated and stirred at 60 ° C. for 3 hours. Next, when the mixed solution was returned to room temperature (20 to 25 ° C.) and allowed to stand for 1 hour, the highly conductive composite composed of PEDOT-PSS precipitated in the mixed solution was precipitated, and the upper layer (supernatant) was formed. It became a transparent liquid.
Next, 5.0 g of 1,2-epoxy-4-vinylcyclohexane was added to the mixture and stirred for 1 hour, and 1,2-epoxy-4-vinylcyclohexane was added to the precipitate of the highly conductive composite. I let you.
Subsequently, by filtration, 2.5 g of a highly conductive composite to which the epoxy compound was added was obtained. The separation of the highly conductive composite by this filtration treatment was completed in 5 minutes or less.
The highly conductive composite collected by filtration was washed with 100 g of acetone and dried. 472.5 g of isopropanol was added to 2.5 g of this highly conductive composite and dispersed with a high-pressure homogenizer to obtain an isopropanol dispersion of the highly conductive composite. Next, a part of the above isopropanol dispersion was applied onto a PET film (Lumilar T60 manufactured by Toray Industries, Inc.) using a # 14 bar coater, and dried at 150 ° C. for 1 minute to obtain a conductive film. Table 1 shows the results of measuring the surface resistance value of the obtained conductive film.

(Example 3)
A mixed solution prepared by adding 15.0 g of methanol and 200 g of methyl ethyl ketone to 100 g (solid content 1.2 g) of the PEDOT-PSS aqueous dispersion of Production Example 2 was heated and stirred at 60 ° C. for 3 hours. Next, when the mixed solution was returned to room temperature (20 to 25 ° C.) and allowed to stand for 1 hour, the highly conductive composite composed of PEDOT-PSS precipitated in the mixed solution was precipitated, and the upper layer (supernatant) was formed. It became a transparent liquid.
Next, 5.0 g of glycidol was added to the mixture and stirred for 1 hour to add glycidol to the precipitate of the highly conductive composite.
Subsequently, by filtration, 2.5 g of a highly conductive composite to which the epoxy compound was added was obtained. The separation of the highly conductive composite by this filtration treatment was completed in 5 minutes or less.
The highly conductive composite collected by filtration was washed with 100 g of acetone and dried. 472.5 g of isopropanol was added to 2.5 g of this highly conductive composite and dispersed with a high-pressure homogenizer to obtain an isopropanol dispersion of the highly conductive composite. Next, a part of the above isopropanol dispersion was applied onto a PET film (Lumilar T60 manufactured by Toray Industries, Inc.) using a # 14 bar coater, and dried at 150 ° C. for 1 minute to obtain a conductive film. Table 1 shows the results of measuring the surface resistance value of the obtained conductive film.

(Example 4)
A mixed solution prepared by adding 15.0 g of methanol and 200 g of methyl ethyl ketone to 100 g (solid content 1.2 g) of the PEDOT-PSS aqueous dispersion of Production Example 2 was heated and stirred at 60 ° C. for 3 hours. Next, when the mixed solution was returned to room temperature (20 to 25 ° C.) and allowed to stand for 1 hour, the highly conductive composite composed of PEDOT-PSS precipitated in the mixed solution was precipitated, and the upper layer (supernatant) was formed. It became a transparent liquid.
Next, 5.0 g of triglycidyl isocyanurate was added to the mixture and stirred for 1 hour to add triglycidyl isocyanurate to the precipitate of the highly conductive composite.
Subsequently, by filtration, 2.5 g of a highly conductive composite to which the epoxy compound was added was obtained. The separation of the highly conductive composite by this filtration treatment was completed in 5 minutes or less.
The highly conductive composite collected by filtration was washed with 100 g of acetone and dried. 472.5 g of isopropanol was added to 2.5 g of this highly conductive composite and dispersed with a high-pressure homogenizer to obtain an isopropanol dispersion of the highly conductive composite. Next, a part of the above isopropanol dispersion was applied onto a PET film (Lumilar T60 manufactured by Toray Industries, Inc.) using a # 14 bar coater, and dried at 150 ° C. for 1 minute to obtain a conductive film. Table 1 shows the results of measuring the surface resistance value of the obtained conductive film.

(Example 5)
A mixed solution prepared by adding 15.0 g of methanol and 200 g of methyl ethyl ketone to 100 g (solid content 1.2 g) of the PEDOT-PSS aqueous dispersion of Production Example 2 was heated and stirred at 60 ° C. for 3 hours. Next, when the mixed solution was returned to room temperature (20 to 25 ° C.) and allowed to stand for 1 hour, the highly conductive composite composed of PEDOT-PSS precipitated in the mixed solution was precipitated, and the upper layer (supernatant) was formed. It became a transparent liquid.
Next, 5.0 g of diallyl monoglycidyl isocyanurate was added to the mixture and stirred for 1 hour to add diallyl monoglycidyl isocyanurate to the precipitate of the highly conductive complex.
Subsequently, by filtration, 2.4 g of a highly conductive composite to which the epoxy compound was added was obtained. The separation of the highly conductive composite by this filtration treatment was completed in 5 minutes or less.
The highly conductive composite collected by filtration was washed with 100 g of acetone and dried. 472.6 g of isopropanol was added to 2.4 g of this highly conductive composite and dispersed with a high-pressure homogenizer to obtain an isopropanol dispersion of the highly conductive composite. Next, a part of the above isopropanol dispersion was applied onto a PET film (Lumilar T60 manufactured by Toray Industries, Inc.) using a # 14 bar coater, and dried at 150 ° C. for 1 minute to obtain a conductive film. Table 1 shows the results of measuring the surface resistance value of the obtained conductive film.

(Example 6)
A conductive film was prepared in the same manner as in Example 1 except that isopropanol was changed to methyl ethyl ketone in Example 1 to obtain a highly conductive complex methyl ethyl ketone dispersion, and the surface resistance value thereof was measured. The results are shown in Table 1.

(Example 7)
50 g (solid content 0.24 g) of the highly conductive composite isopropanol dispersion obtained in Example 1 was mixed with 10 g of Art Resin UN-904M (manufactured by Negami Kogyo Co., Ltd., urethane acrylate, solid content 80%, methyl ethyl ketone solution). , Pentaerythritol triacrylate (30 g), hydroxyethyl acrylamide (2.5 g), diacetone alcohol (10 g), and Irgacure 184 (manufactured by BASF, photopolymerization initiator) (1.6 g) were added and mixed by stirring to obtain a coating material. Subsequently, the paint is applied onto a PET film (Toray Industries, Inc., Lumirror T60) using a # 16 bar coater, dried at 100 ° C. for 1 minute, and irradiated with ultraviolet rays of 400 mJ to form a conductive film. Obtained. The surface resistance value of the hard coat type conductive film thus obtained was measured. The results are shown in Table 1.

(Comparative Example 1)
A mixed solution prepared by adding 215 g of isopropanol to 100 g (solid content 1.2 g) of the PEDOT-PSS aqueous dispersion of Production Example 2 was heated and stirred at 60 ° C. for 3 hours. Next, the mixed solution was returned to room temperature and allowed to stand for 1 hour, but it was confirmed that the conductive composite did not precipitate and the mixed solution was uniform. To this mixed solution, 5.0 g of butylene oxide was added and stirred for 1 hour to add butylene oxide to the conductive composite and precipitate it. Subsequently, by filtration, 2.0 g of the conductive composite to which the epoxy compound was added was obtained. It took 5 hours to separate the precipitates by this filtration treatment.
The conductive composite collected by filtration was washed with 100 g of acetone and dried. 473.0 g of isopropanol was added to 2.0 g of this conductive composite and dispersed with a high-pressure homogenizer to obtain an isopropanol dispersion of the conductive composite. Next, a part of the above isopropanol dispersion was applied onto a PET film (Lumilar T60 manufactured by Toray Industries, Inc.) using a # 14 bar coater, and dried at 150 ° C. for 1 minute to obtain a conductive film. Table 1 shows the results of measuring the surface resistance value of the obtained conductive film.

(Comparative Example 2)
A precipitate was formed in the same manner as in Comparative Example 1 except that 5.0 g of butylene oxide was changed to 5.0 g of 1,2-epoxy-4-vinylcyclohexane in Comparative Example 1. Subsequently, by filtration, 2.1 g of the conductive composite to which the epoxy compound was added was obtained. It took 5 hours to separate the precipitates by this filtration treatment.
The conductive composite collected by filtration was washed with 100 g of acetone and dried. 472.9 g of isopropanol was added to 2.1 g of this conductive composite and dispersed with a high-pressure homogenizer to obtain an isopropanol dispersion of the conductive composite. Next, a part of the above isopropanol dispersion was applied onto a PET film (Lumilar T60 manufactured by Toray Industries, Inc.) using a # 14 bar coater, and dried at 150 ° C. for 1 minute to obtain a conductive film. Table 1 shows the results of measuring the surface resistance value of the obtained conductive film.

(Comparative Example 3)
An attempt was made to generate a precipitate in the same manner as in Comparative Example 1 except that 5.0 g of butylene oxide was changed to 5.0 g of glycidol in Comparative Example 1. However, since no precipitate was formed, the production of the conductive film was stopped.

(Comparative Example 4)
A precipitate was formed in the same manner as in Comparative Example 1 except that 5.0 g of butylene oxide was changed to 5.0 g of triglycidyl isocyanurate in Comparative Example 1, and filtration was attempted. However, the filter paper was clogged and the precipitate could not be filtered out even after spending 5 hours, so that the production of the conductive film was stopped.

(Comparative Example 5)
A precipitate was formed in the same manner as in Comparative Example 1 except that 5.0 g of butylene oxide was changed to 5.0 g of diallyl monoglycidyl isocyanurate in Comparative Example 1. Subsequently, by filtration, 2.2 g of the conductive composite to which the epoxy compound was added was obtained. It took 5 hours to separate the precipitates by this filtration treatment.
The conductive composite collected by filtration was washed with 100 g of acetone and dried. 472.8 g of isopropanol was added to 2.2 g of this conductive composite and dispersed with a high-pressure homogenizer to obtain an isopropanol dispersion of the conductive composite. Next, a part of the above isopropanol dispersion was applied onto a PET film (Lumilar T60 manufactured by Toray Industries, Inc.) using a # 14 bar coater, and dried at 150 ° C. for 1 minute to obtain a conductive film. Table 1 shows the results of measuring the surface resistance value of the obtained conductive film.

<Evaluation>
Table 1 shows the results of measuring the surface resistance values of the conductive films of each example. A resistivity meter (High Restor manufactured by Mitsubishi Chemical Analytech Co., Ltd.) was used for the measurement, and the applied voltage was set to 10 V. The measurement results are shown in Table 1. In addition, "Ω / □" in the table means ohmper square. In addition, "1.0E + 05" represents the "1.0 × 10 ^5".
The smaller the surface resistance value (unit: Ω / □), the higher the conductivity.

From the above results, it is clear that the production method according to the present invention can easily separate the hydrophobized highly conductive composite by filtration. Further, the highly conductive composite obtained by the production method according to the present invention can be easily dispersed in an organic solvent, and the conductive layer of the composition (paint) containing the highly conductive composite is composed of a conductive layer. It is clear that the layer has excellent conductivity.

Claims (16)

A mixed solution of an aqueous dispersion of a conductive complex containing a π-conjugated conductive polymer and a polyanion and an organic solvent is obtained, and the highly conductive complex is precipitated in the mixed solution.
A method for producing a highly conductive composite, which comprises preparating the highly conductive composite to which the epoxy compound is added by adding an epoxy compound to the mixture. The method for producing a highly conductive composite according to claim 1, wherein the content of the organic solvent contained in the mixed solution is 50% by mass or more with respect to the total mass of the mixed solution. The method for producing a highly conductive composite according to claim 1 or 2, wherein the organic solvent contains at least one of a ketone solvent and an alcohol solvent. The method for producing a highly conductive composite according to claim 3, wherein the organic solvent contains a ketone solvent, and the ketone solvent contains methyl ethyl ketone. The method for producing a highly conductive composite according to claim 3, wherein the organic solvent contains an alcohol solvent and the alcohol solvent contains methanol. The method for producing a highly conductive composite according to claim 1 or 2, wherein the organic solvent contains methyl ethyl ketone and methanol. The method for producing a highly conductive composite according to any one of claims 1 to 6, wherein when the highly conductive composite is precipitated in the mixed liquid, the mixed liquid is heated to 40 ° C. or higher. When the highly conductive composite is precipitated in the mixed solution, the content of at least one of the acids and bases other than the polyanion in the mixed solution is 0.1 mass by mass with respect to the total mass of the mixed solution. % Or less, the method for producing a highly conductive composite according to any one of claims 1 to 7. The method for producing a highly conductive composite according to any one of claims 1 to 8, wherein the method for separating the highly conductive composite to which the epoxy compound is added is filtration. The method for producing a highly conductive composite according to any one of claims 1 to 9, wherein the π-conjugated conductive polymer is poly (3,4-ethylenedioxythiophene). The method for producing a highly conductive composite according to any one of claims 1 to 10, wherein the polyanion is polystyrene sulfonic acid. A method for producing an organic solvent dispersion of a highly conductive composite, which comprises mixing the highly conductive composite obtained by the production method according to any one of claims 1 to 11 with an organic solvent. The method for producing an organic solvent dispersion of a highly conductive composite according to claim 12, further comprising mixing a binder component. The method for producing an organic solvent dispersion of a highly conductive composite according to claim 13, wherein the binder component is a compound that forms an acrylic resin after curing. The organic solvent dispersion of the highly conductive composite obtained by the production method according to any one of claims 12 to 14 is applied to at least one surface of the film substrate, and the formed coating film is dried. A method for producing a conductive film, including the process of making a conductive film. Conductivity provided on at least one surface of the film base material with a conductive layer made of a cured layer of an organic solvent dispersion of a highly conductive composite obtained by the production method according to any one of claims 12 to 14. Sex film.